Manufacture of multicolor photographs



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Patented Nov. 7-, 1939 PATENT 0F 2,179,234 Fl CE MANUFACTURE OFMULTICOLOR PHOTOGRAPHS Wilhelm Schneider, Dessau, Germany, assignor, bymesne assignments, to Agfa Ansco 001130! ration, Binghamton, N.

Delaware Y., a corporation of No Drawing. Application September 11,1936,

Serial No., 100,319. 1935 In Germany October 3,

r 4 Claims. .(01. 95-2) My present invention relates to the manufactureof multicolor photographs.

One of its objects is an improved process of producing multicolorphotographs. Another object is a process of producing a multicolorphotograph by a single development in color. Another object is a processof producing a multicolor photograph by a single exposure and a singledevelopment in color. Further objects will be seen 7 from the detailedspecification following hereafter.

It has long been known that one can develop exposed photographic silverhalide emulsions to a color-picture instead of the usual blacksilverpicture by using either certain developers (pyrogallol, indoxyl,thioindoxyl or thelike) which are oxidized to sparingly soluble coloredbodies by exposed silver halide, or by adding to certain developers, forexample para-dimethyl-aminoaniline, substances which couple to formsparingly soluble colored bodies with the oxidation products of thedeveloper produced during'the development. In the latter case it hasbeen proposed to incorporate the coupling components in the sensitivelayer itself. these processes have been conceived particularly for thepurpose of multicolor photography, they have not passed into practicebecause they are much too detailed. For this reason, lately a variantofthe second process referred to above has been proposed, which requires alarge number of successive treatments with liquid of a three-layer film.I

The present invention relates to the treatment of a photographic layerin a simple manner to produce two-color or multicolor pictures withoutany developing operation in excess'of that for normal black-a'nd-whitedevelopment.

Layers suitable for the invention are of the kind which have beendescribed in the co-pending application Ser. No. 90,726 filed July 15,1936. They are silver halide emulsions, to which has been added, forexample, a substance obtainable by the reaction of a compound which byknown reactions is capable of forming dyestuffs, for example an amine, aphenol, an aminophenol, a naphthol or an amino-n'aphthol, or a compoundhaving a reactive methylene-group, with a highly polymeric carboxylicacid or a derivative thereof, for instance, the condensation productfrom U polyvlnyl-maleic-acid-anhydride and p-amino-.phenyl-3-methylpyrazolon having probably the formula:

(on on-on-on), coon com;

and the condensation product from polyvinyl- Although, obviously,

maleic-acid-anhydride and m-arninophenol having probably the formula(on-oH-on-on coon ,OONH- So also the silver halide emulsion layersdescribed in the copending application Ser. No. 72,718 filed April 11,1936, may be used. These contain as coupling components for the colordevelopment such compounds as are fast to diiiusion in the binding agentused, for instance the gelatin or the like. Suitable groups whichdetermine such fastness to diffusion are, for instance, diphenyl,stilbene, azoxy-benzene, hydroxynaphthoic acid amide, diaryl-urea,benzthiazole and certain phenols, aminophenols containing substituentsin the 3:5-position and the like. Color-forming components in whichthese groups are introduced are, for example, phenols, anilines,naphthols,

naphthylamines, amino-naphthols; also all substances which have areactive methylene-group, for example an acetoacetic ester, acyanoacetic ester, a benzoyl-acetic ester, hydrindene, pyrazolone,cumaranone. Further suitable components are for instancea-hydroxynaphthoic-acid-benzi- [m hydroxyphenylaminocarboyll diphenyl orthe like.

Finally, there are applicable according to the invention emulsion layersin which there are incorporated color-formers containing an aliphatichydrocarbon chain of more than 5 carbon atoms. Such layers are describedin the co-pending application Ser. No. 94,340 filed August 5, 1936. All

these layers have the property that the incorporated color-former isconverted into dyestuff by 'a secondary process during the color development and is more strongly held in the light-sensitive layer, whichgenerally comprises gelatin, than has been the case with the bodieshitherto proposed for the purpose; thus they withstand the usualphotographic baths. treatment nor inthe subsequent washing with waterare they dissolved or washed off. Only under these conditions is itpossible to conduct in a single operation a development of all thecontributory colors in three superimposed layers.

In the process there is provided a multilayer Neither in this filmconsisting, for instance of two or three lightsensitive layers arrangedon oneor both faces of a' single support and selectivelycolor-sensitized,

and capable of being developed to a color corresponding with its rangeof color sensitivity; this film is exposed in a photographic orcinematographic camera and then developed with 2. normal black and whitedeveloper to produce a nega tive. For this development there must onlybe used a developer which does not react with the coupling componentsincorporated in the layers, for instance, ,amidol,para-methylaminophenol, or hydroquinone. After the development of theblack and white negative the film, without being fixed, .is exposed tothe general illumination, whereupon the residual silver halide isdeveloped with a color-forming developer, ,for instancepara-dimethylamino-aniline. The general illumination and colordevelopment following the first black-and-white development mayadvantageously be combined by merely conducting the color development inbright light.

In the second developing operation there is produced in each layer ofthe multicolor film a picture in the component color allotted to thislayer; for example, in a 3-layer film there are obtained at once 3component pictures of correct color and superimposed. After the seconddevelopment the silver present in the layers may be removed by any ofthe usual solvents for silver. It is also possible to remove already thesilver formed in the first developing operation by means of the knownsilver dissolving agents.

.The process may similarly be conducted for producing copies by copying,optically or in contact, an exposed film made by the process abovedescribed, enlargement or diminuation being used if desired, on such amaterial and developing to a colored positive picture in the mannerdescribed.

As a specific example, a support, for instance a Celluloid film, carrieson its front face an orthochromatically color-sensitized layer in whichincorporateddiphenylcarboyl-4.4'-di-(paraamino-1-phenyl-3-methyl-5-pyrazolone) as ared developing component. Over this layer is a not specially sensitizedlayer which contains as the yellow developing componentdibenzoylaceticbenzidide-3.3-dicarboxylic acid and at the same time ayellow filter color, for example tartrazine. On the back of the film isa layer of emulsion which is sensitive to red light and contains as theblue developing component 4.4"-di-1-hydroxy-2- naphthoylamino)-diphenyl. Then this film is exposed and first developed for 10 minutesin an amidol developer (200 cc. of water, 1 gram of amidol, 10 grams ofsodium sulfite crystals, 0.2

gram of potassium bromide) and then washed for 5 minutes and furtherdeveloped for 10 minutes in daylight with dimethylaminoaniline (200 cc.of water, Zgrams dimethylaminoaniline, 6 grams calcined sodiumcarbonate); after washing for 15 minutes and then removing silver bymeans of Farmer's reducer, for example 200 cc. of water, 20 grams ofsodium thiosulfate and 2 grams of potassium ferri-cyanide, a coloredpositive is obtained.

What I claim is:

1. A process of producing multicolor photographs which comprisesproducing a multilayer film having incorporated in the several gelatinesilver halide emulsion layers a dye component capable of forming a dyewith a developer adapt- -solved form of diffusing components andremoving the developed silver from said film.

2. A process of producing multicolor photographs which comprisesproducing a multilayer film having the emulsion layers arranged insuperposition 0n the same side of the support and having incorporated inthe several gelatine silver halide emulsion layers a dye componentcapable of forming a dye with a developer adapted for color developmentsaid dye components although soluble in aqueous photographic developingsolutions being of such molecular constitution that they are incapablein such dissolved form of diffusing in gelatine in any photographictreating bath, exposing said multilayer film to a coloredobject,-developing the exposed film in a developer not capable offorming a color with said dye components, exposing said multilayer filma second time simultaneously developing all the layers of the exposedfilm in a developer capable of forming dyes with said dye components andremoving the developed silver from said film.

3. A process of producing multicolor photographs which comprisesproducing a multilayer film having incorporated in the several gelatinesilver halide emulsion layers a dye component capable of forming a dyewith a developer adapted for color development, said dye componentsalthough soluble in aqueous photographic developing solutions being ofsuch molecular con-.

stitution that they are incapable in such disin gelatine in anyphotographic treating bath, exposing said multilayer film to a coloredobject, developing the exposed film in a developer not capable offorming a color with said dye components, and then simultaneouslydeveloping all the layers of said film in bright light in a developercapable of forming a dye with said dye components and removing thedeveloped silver from said film.

4. A process of producing multicolor photographs which comprisesproducing a film having one side coated with an orthochromaticallysensitized silver halide emulsion layer containing diphenyl 4.4" (paraamino 1 phenyl 3 methyl-5-pyrazolone) and this emulsion layer with asilver halide emulsion layer which has not been specially sensitized andcontaining dibenzoylacetic-benzidide-3.3-dicarboxylic acid and a.

yellow filter dye, and the other side with a silver halide emulsionlayer sensitized to red and con taining 4.4-di-(1hydroxy-2-naphthoylamino)- diphenyl, exposing this film to a coloredobject,

simultaneously developing all the layers of the

